Polyurethane polymers are prepared by reacting a di- or polyisocyanate with a polyfunctional, isocyanate-reactive compound, in particular, hydroxyl-functional polyether polyols. Numerous art-recognized classes of polyurethane polymers exist, for example cast elastomers, polyurethane RIM, microcellular elastomers, and molded and slab polyurethane foam. Each of these varieties of polyurethanes present unique problems in formulation and processing.
Two of the highest volume categories of polyurethane polymers are polyurethane molded and slab foam. In slab foam, the reactive ingredients are supplied onto a moving conveyor and allowed to rise freely. The resulting foam slab, often 6 to 8 feet (2 to 2.6 m) wide and high, may be sliced into thinner sections for use as seat cushions, carpet underlay, and other applications. Molded foam may be used for contoured foam parts, for example, cushions for automotive seating.
In the past, the polyoxypropylene polyether polyols useful for slab and molded foam applications have been prepared by the base-catalyzed propoxylation of suitable hydric initiators such as propylene glycol, glycerine, sorbitol, etc., producing the respective polyoxypropylene diols, triols, and hexols. As is now well documented, a rearrangement of propylene oxide to allyl alcohol occurs during base-catalyzed propoxylation. The monofunctional, unsaturated allyl alcohol bears a hydroxyl group capable of reaction with propylene oxide, and its continued generation and propoxylation produces increasingly large amount of unsaturated polyoxypropylene monols having a broad molecular weight distribution. As a result, the actual functionality of the polyether polyols produced is lowered significantly from the "normal" or "theoretical" functionality. Moreover, the monol generation places a relatively low practical limit on the molecular weight obtainable. For example, a base catalyzed 4000 Da (Dalton) molecular weight (2000 Da equivalent weight) diol may have a measured unsaturation of 0.05 meq/g, and will thus contain 30 mol percent unsaturated polyoxypropylene monol species. The resulting actual functionality will be only 1.7 rather than the "nominal" functionality of 2 expected for a polyoxypropylene diol. As this problem becomes even more severe as molecular weight increases, preparation of polyoxypropylene polyols having equivalent weights higher than about 2200-2300 Da is impractical using conventional base catalysis.
Double metal cyanide ("DMC") complex catalysts such as zinc hexacyanocobaltate complexes were found to be catalysts for propoxylation about 30 years ago. However, their high cost, coupled with modest activity and the difficulty of removing significant quantities of catalyst residues from the polyether product, hindered commercialization. The unsaturation level of polyoxyproylene polyols produced by these catalysts was found to be low, however.
The relatively modest polymerization activity of these conventional double metal cyanide-complex catalysts has been recognized as a problem by workers in the field. One method of improving polyether polyol yields obtained from such catalysts is proposed in U.S. Pat. No. 4,472,560. This publication proposes a process for epoxide polymerization using as a catalyst a double metal cyanide-type compound, wherein said process is carried out in the presence of one or more non-metal containing acids of which a 0.1N solution in water at 25.degree. C. has a pH not exceeding 3. The acid is introduced as a solution in an appropriate solvent with stirring into a suspension of a double metal cyanide-metal hydroxide complex. After evaporation of volatile compounds, the solid thus obtained is used or stored for use as a polymerization catalyst without any filtration or centrifugation. Example 1 of the patent illustrates the preparation of a solid catalyst containing approximately 1 HCl per mole of Zn.sub.3 [Co(CN).sub.6 ].sub.2. Example 16 shows that the yield of polyether polyol is improved about 90% when 2 HCl per mole of Zn.sub.3 [Co(CN).sub.6 ].sub.2 ZnCl.sub.2 is present. No mention is made of the effect of the acid on other characteristics of the polyether polyol, such as the amount of high molecular weight tail.
Recently, as indicated by U.S. Pat. Nos. 5,470,813, 5,482,908, 5,545,601, and 5,712,216, researchers at ARCO Chemical Company have produced substantially noncrystalline or amorphous DMC complex catalysts with exceptional activity, which have also been found to be capable of producing polyether polyols having unsaturation levels in the range of 0.002 to 0.007 meq/g (levels previously obtainable only through the use of certain solvents such as tetrahydrofuran). The polyoxypropylene polyols thus prepared were found to react in a quantitatively different manner from prior "low" unsaturation polyols in certain applications, notably cast elastomers and microcellular foams. However, substitution of such polyols for their base-catalyzed analogs in molded and slab foam formulations is not straightforward. In molded foams, for example, foam tightness increases to such an extent that the necessary crushing of the foams following molding is difficult if not impossible. In both molded foams and slab foams, foam collapse often occurs, rendering such foams incapable of production. These effects occur even when the high actual functionality of such polyols is purposefully lowered by addition of lower functionality polyols to achieve an actual functionality similar to that of base-catalyzed polyols.
DMC-catalyzed polyoxypropylene polyols have exceptionally narrow molecular weight distribution, as can be seen from viewing gel permeation chromatograms of polyol samples. The molecular weight distribution is often far more narrow than analogous base-catalyzed polyols, particularly in the higher equivalent weight range, for example. Polydispersities less than 1.5 are generally obtained, and polydispersities in the range of 1.05 to 1.15 are common. In view of the low levels of unsaturation and low polydispersity, it was surprising that DMC-catalyzed polyols did not prove to be "drop-in" replacements for base-catalyzed polyols in polyurethane foam applications. Because propoxylation with modern DMC catalysts is highly efficient, it would be very desirable to be able to produce DMC-catalyzed polyoxypropylene polyols which can be used in slab and molded polyurethane foam applications without causing excessive foam tightness or foam collapse.
Surprisingly, when one or more molar equivalents of an acid such as hydrochloric acid are combined with a highly active, substantially noncrystalline double metal cyanide complex catalyst of the type described in U.S. Pat. Nos. 5,470,813, 5,482,908, 5,545,601 and 5,712,216, complete deactivation of the catalyst is observed. This result was unexpected in view of the teaching of U.S. Pat. No. 4,472,560 that such acids will function as promoters for conventional double metal cyanide complex catalysts.